Insecticidal N-aralkanoyl and N-aralkenoyl derivatives of O,S-dihydrocarbylphosphoroamidothioates and S,S-dihydrocarbylphosphoroamidodithioates

ABSTRACT

N-aralkanoyl and N-aralkenoyl derivatives of S,S-dihydrocarbyl phosphoroamidodithioates and O,Sdihydrocarbylphosphoroamidothioates have a high degree of insecticidal activity with relatively low mammalian toxicity.

O Unlted States Patent [1 1 [111 3,885,032

Magee May 20, 1975 INSECTICIDAL N-ARALKANOYL AND [51] Int. Cl A0ln 9/36 N-ARALKENOYL DERIVATIVES ()F [58] Field of Search 424/219, 220, 212 O,S-DIHYDROCARBYLPHOS- PHOROAMIDOTHIOATES AND References Cited S,S-DIHYDROCARBYLPHOS- UNITED STATES PATENTS PHOROAMIDODITHIOATES 3,201,446 8/1965 Tolkrith 260/959 Inventor: Philip S. Magee, lgnatio, Calif: 3,825,634 7/1974 Magee 260/959 [73] Assignee: Chevrpn Research Company, San Primary Examiner Albert Meyers Franclsco, Cahf- Assistant Examiner-Douglas W. Robinson [22] Filed: June 14, 1974 Attorney, Agent, or Firm-G. F. Magdeburger; Dix A.

Newell; Raymond Owyang [21] Appl. No.: 479,344

Related U.S. Application Data [57] ABSTRACT [60] Division of Ser. No. 317,476, Dec. 21, 1972, Pat. No. N-aralkanoyl and N-aralkenoyl derivatives of 5,8- 3,325,634, Which is a Continuation-impart 0f N dihydrocarbyl phosphoroamidodithioates and 0,8- 3,846, e 1970 3,716,600, which 15 a dihydrocarbylphosphoroamidothioates have a high decommuanonmpart of 810,383 March gree of insecticidal activity with relatively low maml969' abandoned malian toxicity.

52 12 Claims, No Drawings U.S. Cl. 424/212; 424/219; 424/220 INSECTICIDAL N-ARALKANOYL AND N-ARALKENOYL DERIVATIVES OF 0,. -DIHYDROCARBYLPHOSPI-IOROAMIDOTHIO- A'TES AND S,S-DIHYDROCARBYLPHOSPI-IOROAMIDODITHI OATES CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of U.S. Ser. No. 13,846, filed Feb. 24, 1970, now U.S. Pat. No. 3,716,600, which, in turn, is a continuation-in-part of US. Ser. No. 810,383, filed Mar. 25, 1969, now abandoned.

DESCRIPTION OF THE PRIOR ART as insecticides. L. Almasi et a1, Chem. Ber. 100 2626 (1967) and Chem. Ber. 99 3293 (1966), disclose O- ethyl-S-methyl-N-benzoylphosphoroamidothioate, O- ethyl-S-methyl-N-p-chlorobenzoylphosphoroamidothioate and O-ethyl-S-methyl-N-p-methylbenzoylphosphoroamidothiate.

DESCRIPTION OF THE INVENTION The phosphoroamidothiates and phosphoroamidodithioates of this invention are represented by the formula (I) II .R-Y 2 1 P N R S \R3 wherein R and R individually are alkyl, alkenyl or alkynyl of up to 6 carbon atoms, R is aralkyl or aralkenyl of 7 to 10 carbon atoms and up to 2 (0 to 2) fluorine, chlorine or bromine atoms, R is hydrogen or alkyl of l to 6 carbon atoms and Y is oxygen or sulfur.

Representative alkyl groups which R, R and R may represent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, sec-pentyl and hexyl. Representative alkenyl of 3 to 6 carbon atoms which R and R may represent include allyl, 2-butenyl, isobutenyl, 3-hexenyl, etc. Representative alkynyl of 3 to 6 carbon atoms which R and R may represent include 2- propynyl, Z-butynyl, 3-hexynyl, etc. Preferred R and R groups are alkyl of 1 to 3 carbon atoms, especially methyl. The preferred R group is hydrogen.

Representative phenylalkyl R groups of 7 to 10 carbon atoms include benzyl, Z-phenylethyl, 3-tolylpropyl, 4-phenylbutyl, etc. Representative phenylalkenyl R groups of 8 to 10 carbon atoms include styryl, 3-phenyl-l-propenyl, 4-phenyl-2-butenyl, etc. Representative phenylalkyl and phenylalkenyl substituted in the aromatic moiety with halogens include 2-fluorobenzyl, 4-chlorobenzyl, 2,4-dibromobenzyl, 2-(4- chlorophenyhethyl, 3-(2-fluorophenyl)propyl, 4- fluorostyryl, 3-( 2-fluorophenyl)- 1 -propenyl, 4(4-chlorophenyl)-3-buteny1, etc.

Representative phosphoroamidothioates of formula (I) are O-methyl-S-allyl-N-2-fluorophenylacetylphosphoroamidothioate, O-methyl-S-methyl-N-isopropyl- N-4-bromophenylacetylphosphoroamidothioate, O- allyl-S-allyl-N-2,4-dichlorophenylacetylphosphoroamidothioate, O-propynyl-S-methyl-N-methyl-N- 4-methylphenylacetylphosphoroamidothioate, O-ethyl- S-ethyl-N-3-(4-chlorophenyl)propionylphosphoroamidothioate, O-allyl-S-ethyl-N-3-(2- methylphenyl)propionylphosphoroamidothioate, O- methyl-S-methyl-N-4-phenylbutyrylphosphoroamidothioate, O-isopropyl-S-propyl-N-isopropyl-N-4- phenylbutyrylphosphoroamidothioate, O-methyl-S- methyl-N-methyl-N-4-( 3 chlorophenyl)pentanoylphosphoroamidothioate, O- methyl-S-ethyl-N-cinnamoylphosphoroamidothioate, O-methyl-S-pentyI-N-4-phenyl-but-2-enoylphosphoroamidothioate, O-methyl-S-methyl-N-3-phenylprop-2-enoylphosphoroamidothioate and O-hexyl-S- hexyl-N-cinnamoylphosphoroamidothioate.

Representative phosphoroamidodithioates of .formula (I) are: S-methyl-S-methyl-N-isopropyl-N-2- fluorophenylacetylphosphoroamidodithioate, S- propynyl-S-propynyl-N-4-brom0phenylacetylphosphoroamidodithioate, S-methyI-S-alIyl-N-methyl-N- 2,4-dichlorophenylacetylphosphoroamidodithioate, S-methyl-S-methyl-N-4-methylphenylacetylphosphoroamidodithioate, S-ethyl-S-ethyl-N-3-(4- chlorophenyl)propionylphosphoroamidodithioate, S- methyl-S-ethyl-N-3-(2-methylphenyl)propionylphosphoroamidodithioate, S-methyl-S-methyl-N-4- phenylbutyrylphosphoroamidodithioate, S-isopropyl-S- propyl-N-4-phenylbutyrylphosphoroamidodithioate, S-methy1-S-methyl-N-4-(3- chlorophenyl)pentanoylphosphoroamidodithioate, S- methyl-S-ethyl-N-cinnamoylphosphoroamidodithioate, S-allyl-S-pentyl-N-4-phenylbut-2-enoylphosphoroamidodithioate, S-allyl-S-a1lyl-N-3-phenylprop- 2-enoylphosphoroamidodithioate and S-hexyl-S-hexyl- N-cinnamoylphosphoroamidodithioate.

The preferred compounds of formula I are O,S- dialkyl-N-aralkanoylphosphoroamidothioates wherein R and R are alkyl of l to 3 carbon atoms, R is phenylalkyl substituted on the phenyl moiety with up to 2 fluorine, chlorine or bromine atoms, and R is hydrogen.

The compounds of formula I may be prepared by actylating an appropriate O-hydrocarbyl-S- hydrocarbylphosphoroamidothioate or S-hydrocarbyl- S-hydrocarbylphosphoroamidodithioate. O-alkyl-S- alkylphosphoroamidothioates and their preparation are disclosed in US. Pat. No. 3,309,266. O-alkyl-S- unsaturated hydrocarbyl phosphoroamidothioates and their preparation are disclosed in U.S. Pat. No. 3,649,723.

Conventional acylating agents, such as acyl halides, ketenes and acid anhydrides and conventional acylating conditions may be used in this reaction. In the case I wherein R represents an alkylating agent correspondof N-aralkanoyl compounds, aralkanoyl chlorides are ing to R This acylation may be carried out by the same preferred acylating agents. techniques described above for the acylation reaction This acylation reaction (illustrated with an acy] haldepicted in equation (1). The acylation reaction (2) is ide as the acylating agent) may be represented by the 5 also described in applicants U.S. Ser. No. 148,139, following equation: filed May 28, 1971. The reaction between the N-acyl- II RY 0 v 0 o -R t RY v+ P NH R -C-C1 P N I-lCl (1) 1 a R s R R 8 R (II) (III) (IV) wherein R, R, R R and Y have the same significance phosphoroamidothionate and the alkylating agent may as previously defined. be done according to the procedures described in US.

This acylation will usually be carried out at about 0 Pat. No. 3,309,266 for reacting 0,0-dialkylphosto 60C. in the presence of solvents such as methylene 20 phoroamidothionate with an alkylating agent.

chloride, chloroform, tetrahydrofuran and benzene. Pressure is not critical in this reaction. For convenience, atmospheric or autogenous pressure will be used. Under normal conditions, stoichiometric proportions or a slight deficiency of acylating agent will be used. The acylation will usually take 2 to 24 hours to reach completion. The reaction product may be purified by conventional extraction and recrystallization techniques.

N-acylated phosphoroamidothioates of this invention Alternatively, the D y y y p may also be prepared by acylating an appropri t 0,0- 30 phoroamidothioate (VI) can be converted to the O,S- dihydrocarbylphosphoroamidothionate and then isomdihydrocarbylphosphoroamidothioa y treating erizing the resulting N-acylphosphoroamidothionate e 0,0- 0 p0 n with a Sodium lkyl e ap- Suitable alkylating agents represented by R include alkyl, alkenyl and alkynyl halides, particularly iodides,

v e.g., methyl iodide, ethyl iodide, allyl iodide, propargyl 25 iodide, butyl iodide, etc. and dialkyl and dialkenyl sulfates, e.g., dimethyl sulfate, diethyl sulfate, diallyl sulfate and dihexyl sulfate.

with an alkylating agent to produce the O-hydrocarbyld E to m the Odium alt and alkylating S-hydrocarbyl-N-acylphosphoroamidothioate. This re- 35 the S-sodium salt to form the O,S-compound (VII). action scheme is represented (using an acyl chloride as This reaction scheme is represented by the following the acylating agent) by the following equations: equations:

0 s c-R t 2 (RO)2P rim R -C-Cl- (RO) 2P III (2) (v) (n1) (vi) II s /c-R o 0 Y I 6) R0 I (R01 1-1 R1 P N c-R R ('3) i 3 1 I 3 R R s R (VI) (VII) s o I o o H a.

2 4 2 (R0) P 1.- c R R Slla P N c R (u) (v1) vr11 (1x) R s N aS i 1. n

P N c R R1 1 N c R2 (5) R0 R0 l a 3 R v R (ix) (VII) 6 The meialalion reaction depicted in equation is The above reactions are preferably carried out in the conducted by contacting substantially equimolar presence of a weak base, such as the organic amines, amounts of the reactants (VI) and (VIII) in the liquid for example pyridine, dimethyl aniline, triethyl amine,

phase in an inert solvent at a "temperature of etc. The base is preferably present in an amountat least I0-100C. The reaction is complete within hours, 5 equal to the moles of mercaptan. An inert organic solmore usually in 5 .hours or less. The sodium salt product vent, such as diethyl ether, tetrahydrofuran, dioxane, (IX) may be used for further reaction without separadichloromethane, etc. may be present. The reaction tion. The alkylation of the sodium salt (IX) is effected temperatures are generally in the range of 0 to C., by mixing substantially equimolar amounts of the sopreferably 0 to 5C. The reaction time necessary to dium salt (IX) and the alkylating agent R in an inert 10 complete the addition of the mercaptan to the ph0S-. solvent at a temperature in the range of 8()C, f. phorous oxychloride will range from about I to 10 erably 60C. The product v11) is isolated by conhours The y y y y p p ventional methods, e.g., extraction, chromatography, chloridodithioate P can be Purified y distillation, crystallization or chromatography, if desired.

If th acylating agent, The second step of the preparation, i.e., amidation,

is carried out by adding gaseous ammonia or an amine to a solution of the S-hydrocarbyl-S- 2 9 hydrocarbylphosphorochloridodithioate according to R -C-C1 the following equation:

0 0 RS t RS P 01 R llli P NHR n01 10) 1 1 R S R 5 is weak it may be desirable to prepare the compounds wherein R, R and R have the same significance as preof this invention by amidating an appropriate 0,0- viously defined. dihydrocarbylphosphorothiochloridate to obtain 0,0- dihydrocarbyl-N-acylphosphoroamidothioate and re- The reaction is preferably carried out In an inert oracting said N-acylphosphoroamidothioate with an acyl- 3O ganic solvent, such as benzene, toluene, xylene, and the ating agent as described above. This reaction scheme like, at temperatures in the range of 10 to 75C, prefis illustrated by the following set of equations: erably to 60C. Completion of the reaction is indis o s 0 2 2 (R0) -P C1 R -C-1 llli. (R0) -P N -C-R (6) (V) (VI) S O G) O O H II (R0) P u -c-R R P N C-R R (7) R R s R The S-hydrocarbyl-S-hydrocarbylphoscated by cessation of ammonium chloride precipitaphoroamidodithioate can be-prepared by the reaction tion. Following the reaction, the crude product can be of phosphorous oxychloride with a mercaptan followed isolated by filtration and then separated from ammoby amidation of the resulting S-hydrocarbyl-S- nium chloride by selective extraction with a solvent,

hydrocarbylphosphoroamidodithioate. The first step of such as acetone, methanol or similar organic materials. synthesis involves the addition of 2 mols of a mercaptan to 1 mol of phosphorous oxychloride (POCI accord- The 0,0-dihydrocarbylphosphoroamidothioate coming to the following equations (if R and R are the pounds used to prepare the compounds of the invensame, a single reaction can be carried out): tion are prepared by the following reactions:

0 1 O 1 v P RSH7=)RS-P C1 HCl (8) RS-P 'R SH P +uc1 (9) c1 I RS c1 S S l Cl Fl Cl ROI! R P Cl (11) l C1 C1 S S 1- l l 'RO-lf-Cl +R0ll RO-P-Cl (12) I c1 0R S S 3 4 R0 II C1 R NH M R0 Fl NH R (13) OR OR The above reactions (11-13) are conducted by esphoroamidodithioate.

sentially the same procedures described for reactions (8-10).

EXAMPLES The following examples describe methods which may be used to prepare the phosphoroamidothioates of this invention.

EXAMPLE] Preparation of O,S-dimethyl-N-phenylacetylphosphoroamidothioate.

A mixture of 10 g 0,0-dimethyl-N- phenylacetylphosphoroamidothioate, 2 g dimethyl sulfate and 10 ml chloroform was refluxed for 3 hours (7080C). The crude reaction mixture was chromatographed on silica (methylene dichloride/acetone eluants) to give the product. Elemental analysis on the product is tabulated in Table I.

EXAMPLE II Preparation of O,S-dirnethyl-N-3- phenylpropionylphosphoroamidothioate.

This compound was prepared by isomerizing 0,0- dimethyl-N-3-phenylpropionylphosphoroamidothioate with dimethyl sulfate and purified by chromatography on silica by a procedure similar to that of Example I.

Elemental analysis on the compound is tabulated in Table 1.

EXAMPLE III EXAMPLE IV O,S-dimethyl-N-cinnamoylphosphoroamidothioate.

This compound was prepared by isomerizing 0,0- dimethyl-N-cinnamoylphosphoroamidothioate with dimethyl sulfate and purified by chromatography on silica by a procedure similar to that of Example I. Elemental analysis on the compound is tabulated in Table I.

EXAMPLE V Preparation of S,S-dimethyl-N-acetylphos- A solution of 73.2 g (0.48 mole) of phosphorous oxychloride in 300 ml of dry diethyl ether was charged to a 1 liter flask at a temperature of 0C. A solution of 76.2 g (0.96 mole) of pyridine and 49 g (1.0 mole) of methyl mercaptan in 400 ml. of diethyl ether was added slowly to the flask containing phosphorous oxychloride over a 2-hour period of time, maintaining the temperature from 0C. to 5C. The mixture was then stirred for an additional 6 hours at temperatures of 0 to 10C. After 18 hours of standing at 0C. the crude reaction product was separated from the solid residue, stripped of solvent and purified to give 31.7 g of a liquid S,S- dimethylphosphorochloridodithioate.

The above S,S-dimethylphosphorochloridodithioate was then charged with 500 ml of toluene to a 1 liter flask and ammonia gas added slowly at a temperature of 50 to 55C. When the temperature started to drop, ammonia addition was stopped. The reaction was held at 50C. for /a hour and then cooled to room temperature and filtered. The filtrate was stripped of solvent under vacuum, then purified to give 6.6 g of 8,8- dimethylphosphoroamidodithioate. The compound had a melting point of l03l05C., and the following N, S, P analysis:

S,S-dimethylphosphoroamidodithioate was dissolved in 250 ml of dichloromethane and charged to a 500 ml flask. 39.3 g (90.5 mole) of acetylchloride was added. The solution was refluxed for 2 hours and stored at room temperature for 18 hours. The dichloromethane and excess acetylchloride were removed by evaporation and the product dissolved in 250 ml of dichloromethane to which was added 250 ml water containing sufficient calcium hydroxide to give a pH of 7 after thorough mixing. The organic phase was separated from the aqueous phase and S,S-dimethyl-N- acetylphosphoroamidodithioate recovered from the organic phase as an oil (3.7 g). Analysis on the product is tabulated in Table I.

EXAMPLE VI O-allyl-S-methyl-N-acetylphos- Preparation of phoroamidothioate.

A 68 g (1.1 mol) sample of allyl alcohol was added silica (hexane/methylene chloride/acetone eluants) to give the S-methyl-O-allyl-N-acetylphosphoroamidothidropwise to 84 g (0.5 mol) phosphorous thiochloride Gate Product as an Elemental analysis for (PSCl at 10C. The resulting reaction mixture was e n Qa Showedi cooled in a DRY-lCE/acetone bath while 80 g (1 mol) Calculated Found of a 50% sodium hydroxide solution was added. After the addition was completed, the reaction mixture was if: {:2 (I a stirred at about C for We hours, diluted with 200 ml TABLE I Compound Melting Point Elemental Analysis %P %S Calc. Found Calc. Found O,S-dimethylN-phenylacetylphosphoroamidothioate oil l 1.95 12.48 12.35 12.85 O.S-dimethyl-N-3-phenylpropionylphosphoroamidothioate oil 12.72 1 1.72 O,S dimethyl-N p-chlorophenylacetylphosphoroamidothioate 92-94 10.6 9.6 O,S-dimethyl-N-cinnamoylphosphoroamidothioate 98-102 1 1.42 11.42 11.82 1 1.93 S.S-dimethyl-Nacetyl phosphoroamidodithioate oil 15.52 14.08 32.1 31.05 O-allyl-S-methyl-N-acetylphosphoroamidothioate oil 14.8 14.62 15 .4 15 .8

water and 50 ml chloroform. The organic phase was UTILITY separated, dried over magnesium sulfate, filtered and The compounds of this invention were tested as f l. evaporated under reduced pressure- The resldue was lows to illustrate their insecticidal activity. Test results diluted to 31.3 g of 0,0-diallylphosphorochloridothioate, b.p. 72'74C (0.15 mm Hg).

The above 0,0-diallylphosphorochloridothioate (30 g) and 500 m1 benzene were then charged to a flask and ammonia (10 g) in 100 ml benzene was slowly added.

A heavy precipitate was formed in an exothermic reaction. The reaction was evaporated to give a cloudy white liquid. The liquid was diluted with 50 ml of methylene chloride and refluxed with 10 g of ammonium hydroxide for /2 hour. The organic layer was washed with water, dried over magnesium sulfate, filtered and evaporated to give 20 g of 0,0-diallylphosphoroamidothioate.

A 10 g (0.0518 mol) sample of the above 0,0- diallylphosphoroamidothioate, 6 g (0.059 mol) acetic anhydride, ml methylene chloride and 1 ml phosphoric acid was refluxed for 3 hours. The reaction mixture was diluted with ml water and 100 ml aqueous saturated ammonium chloride solution. The aqueous solution was extracted with methylene chloride. The methylene chloride extracts were washed with aqueous ammonium chloride solution, dried over magnesium sulfate and evaporated to give 104 g of 0,0-diallyl-N- acetylphosphoroamidothioate.

A mixture of 10 g (0.0425 mol) of the above 0,0- diallyl-N-acetylphosphoroamidothioate, 4.3 g (0.0425) sodium n-butyl mercaptide and 40 ml methanol was refluxed for 4 hours and then evaporated under reduced pressure to give the crude S-sodium-O-allyl-N- acetylphosphoroamidothioate salt. The salt, 6 g dimethyl sulfate. and 40 ml acetonitrile, were then refluxed for 25 hours. A heavy precipitate formed. The reaction mixture was filtered and the filtrate was evaporated under reduced pressure to give 9 g of a yellow liquid residue. The residue was chromatographed on are reported in Table 11.

Test Procedures Cabbage looper (Trichoplusia ni): An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to 500 ppm. Cabbage leaf sections were dipped in the toxicant solution and dried. The sections were then infested with cabbage looper larvae. Mortality readings were taken after 24 hours.

American Cockroach (Periplaneta americana L.): A 500 ppm acetone solution of the candidate toxicant was placed in a microsprayer (atomizer). A random mixture of anesthetized male and female roaches was placed in a container and 55 mg. of the abovedescribed acetone solution was sprayed on them. A lid was placed on the container. A mortality reading was made after 24 hours.

Houseflies (Musca domestica L): A 500 ppm acetone solution of the candidate toxicant was placed in a microsprayer (atomizer). A random mixture of anesthetized male and female flies was placed in a container and 55 mg. of the above-described acetone'solution was sprayed on them. A lid was placed on the container. A mortality reading was made after 24 hours.

Two-spotted Mites (Telramuchus urticae): An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to ppm. Pinto bean leaves which were infested with mites were dipped in the toxicant solution. Mortality readings were taken after 24 hours.

Aphids (Aphis gossypii Glover): An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to 30 ppm. Cucumber leaves infested with the cotton aphids were 1 1 dipped in the toxicant solution. Mortality readings were then taken after 24 hours.

tacting said insects or their habitats with an insecticidally toxic amount of the compound of the formula TABLE II Compound Mortality Cabbage Looper Cockroach Housefly Mite Aphid O,S-dimethyl-N-phenylacetylphosphoroamidothioate 30 O 99 I00 O,S-dimethyl-N-3-phenylpropionylphosphoroamidothioate 90(625 ppm) 78 0 60 2 O,S-dimethyl-N-p-chlorophenylacetylphosphoroamidothioate 80 39 0 70( 80 ppm) 22 O,S-dimethyl-N-cinnamoylphosphoroamidothioate 94 0 O l 00 O S,S-dimethyl-N-acetylphosphoroamidoiithioate 0 80 l 00 97 O-allyl-S-methyl-N-acetyl- 98 phosphoroamidothioate 90 100 I00 85(40 ppm) 90 In addition to the specific formulations and applica- 0 I t1on techniques described above, one or more of the 2 compounds of this invention may be applied in other R1 S i C R liquid or solid formulations to the insects, their environment or hosts susceptible to insect attack. For example, they may be sprayed or otherwise applied directly to plants or soil so as to effect control of insects coming into contact therewith.

Formulations of the compounds of this invention will comprise a toxic amount of one or more phosphoroamidothioate and/or phosphoroamidodithioate and a biologically inert carrier. Usually they will also contain a wetting agent. Solid carriers such as silica, clay, talc, sawdust and the like may be used in such formulations. Liquid diluents which may be used with these compounds include water and aromatic solvents. In addition these formulations may contain other comparible pesticides, plant growth regulators, fillers, stabilizers, attractants and the like.

The term insecticide and insect as used herein refer to their broad and commonly understood usage rather than to those creatures which in the strict biological sense are classified as insects. Thus, the term insect is used not only to include small invertebrate animals belonging to the class Insecta but also to other related classes of arthropods whose members are segmented invertebrates having more or fewer than six legs, such as spiders, mites, ticks, centipedes, worms and the like.

As will be evident to those skilled in the art, various 5 modifications on this invention can be made or followed, in the light of the foregoing disclosure and discussion, without departing from the spirit or scope of the disclosure or from the scope of the following claims:

I claim:

1. A method of killing insects which comprises conwherein R and R individually are alkyl, alkenyl or alkynyl of up to 6 carbon atoms, R is phenylalkyl or phenylalkenyl of 7 to 10 carbon atoms substituted with up to 2 fluorine, chlorine or bromine atoms, R is hydrogen or alkyl of 1 to 6 carbon atoms and Y is oxygen or sulfur.

2. The method of claim 1 wherein R and R are alkyl of l to 3 carbon atoms, R is hydrogen and Y is oxygen.

3. The method of claim 2 wherein R and R are methyl and R is benzyl.

4. The method of claim 2 wherein R and R are methyl and R is 2-phenylethyl.

5. The method of claim 2 wherein R and R are methyl and R is p-chlorobenzyl.

6. The method of claim 2 wherein R and R are methyl and R is styryl.

7. An insecticidal composition comprising an insecticidally toxic amount of the compound defined in claim 1 and a biologically inert carrier therefor.

8. The composition of claim 7 wherein R and R are alkyl of 1 to 3 carbon atoms, R is hydrogen and Y is oxygen.

9. The composition of claim 8 wherein R and R are methyl and R is benzyl.

10. The composition of claim 8 wherein R and R are methyl and R is 2-phenylethyl.

1 1. The composition of claim 8 wherein R and R are methyl and R is p-chlorobenzyl.

12. The composition of claim 8 wherein R and R are methyl and R is styryl.

UNITED STATES PATENT AND TRADEMARK OFFICE EETIFIQATE F CORRECTION 9 PATENT NO. 3,885,032

DATED May 20, 1975 I PHILIP s. MAGEE It is certified that error appears in the above-identified patent and that said Letters Patent Q are hereby corrected as shown below:

Column 1, line 9 omitted, should read: --is a division of Serial No. 3317, 176, filed December 21, 1972, now U.S. Patent No. 3,825,63 t, which is-- Column 2, lines 57-58 should read --acy1ating-- 1 Column 4, line 1 should read --R 1 Column 4, line 22 should read --R (+3 1 a Column 5, line should read --R Column 5, lines -31 should read --a1ky1ating-- Column 9, line 31 should read --distilled-- Column 9, line 58 should read (0.0 425 mol)-- Table II, Columns 11-12, fifth compound should read --acetylphosphoroamidodithioate-- Table II, Columns 11-12, column 3 "Cockroach", fifth compound a should read --60-- Table II, Columns 11-12, column 5"Mite", third compound should read --(30 ppm)-- Column 11, lines 37-38 should read --compatible-- Engncd and Scaled thus eleventh Of May 1976 [SEAL] Q Arrest:

RUTH C. MASON C. MARSHALL DANN Allvsting Officer ('mmnissimu'r nflau'ms and Trademarks 

1. A METHOD OF KILLING INSECTS WHICH COMPRISES CONTACTING SAID INSECTS OR THEIR HABITATS WITH AN INSECTICIDALLY TOXIC AMOUNT OF THE COMPOUND OF THE FORMULA
 2. The method of claim 1 wherein R and R1 are alkyl of 1 to 3 carbon atoms, R3 is hydrogen and Y is oxygen.
 3. The method of claim 2 wherein R and R1 are methyl and R2 is benzyl.
 4. The method of claim 2 wherein R and R1 are methyl and R2 is 2-phenylethyl.
 5. The method of claim 2 wherein R and R1 are methyl and R2 is p-chlorobenzyl.
 6. The method of claim 2 wherein R and R1 are methyl and R2 is styryl.
 7. An insecticidal composition comprising an insecticidally toxic amount of the compound defined in claim 1 and a biologically inert carrier therefor.
 8. The composition of claim 7 wherein R and R1 are alkyl of 1 to 3 carbon atoms, R3 is hydrogen and Y is oxygen.
 9. The composition of claim 8 wherein R and R1 are methyl and R2 is benzyl.
 10. The composition of claim 8 wherein R and R1 are methyl and R2 is 2-phenylethyl.
 11. The composition of claim 8 wherein R and R1 are methyl and R2 is p-chlorobenzyl.
 12. The composition of claim 8 wherein R and R1 are methyl and R2 is styryl. 